NOR-HALS compounds as flame retardants

ABSTRACT

The present invention relates to the use of NOR-HALS compounds in flame retardant polymer compositions. These compositions are especially useful for the manufacture of flame retardant compositions based on thermoplastic polymers, especially polyolefin homo- and copolymers, polycondensates, such as polyamines or polyesters and duro-plastic polymers, such as polyepoxides.

CROSS-REFERENCE TO RELATED APPLICATIONS

The application is a divisional application of U.S. Ser. No. 15/131,585, filed Apr. 18, 2016, which is a continuation of U.S. Ser. No. 14/379,842, filed Aug. 20, 2014, which is a 371 of PCT/IB2013/052003, filed Mar. 13, 2013, which claims priority to EP 12159919.5, filed Mar. 16, 2012, and claims benefit of provisional to 61/611,620, filed Mar. 16, 2012.

The present invention relates to the use of NOR-HALS compounds in flame retardant polymer compositions. These compositions are especially useful for the manufacture of flame retardant compositions based on thermoplastic polymers, especially polyolefin homo- and copolymers, polycondensates, such as polyamines or polyesters, and duro-plastic polymers, such as polyepoxides.

Flame retardants are added to polymeric materials (synthetic or natural) to enhance the flame retardant properties of the polymers. Depending on their composition, flame retardants may act in the solid, liquid or gas phase either chemically, e.g. as a spumescent by liberation of nitrogen, and/or physically, e.g. by producing a foam coverage. Flame retardants interfere during a particular stage of the combustion process, e.g. during heating, decomposition, ignition or flame spread.

There is still a need for flame retardant compositions with improved properties that can be used in different polymer substrates. Increased standards with regard to safety and environmental requirements result in stricter regulations. Particularly known halogen containing flame retardants no longer match all necessary requirements. Therefore, halogen free flame retardants are preferred, particularly in view of their better performance in terms of smoke density associated with fire. Improved thermal stability and less corrosive behaviour are further benefits of halogen free flame retardant compositions.

NOR-HALS compounds are known from EP 1 731 508 as stabilizers for synthetic resins to protect these substrates from degradation caused by the action of chemicals and acid rain.

It has surprisingly been found that thermoplastic or duroplastic polymers with excellent flame retardant properties are prepared in the event that selected NOR-HALS compounds are added to the polymer substrate.

These compositions have excellent thermal stability and are therefore especially suited for the application in engineering thermoplastics and epoxy laminates used for the manufacture of electrical and electronic parts and devices. By using the instant flame retardant additives in thermoplastic and duroplastic resins, conventional halogen containing flame retardants and halogenated epoxy resins, antimony compounds, and inorganic fillers may largely be reduced or replaced.

The present invention relates to the use of a NOR-HALS compound of the formula

-   -   Wherein     -   R₁ and R₂ represent C₁-C₃₀alkyl,     -   for inducing the flame retardancy in polymers.

Examples of C₁-C₃₀alkyl groups represented by R₁ and R₂ in the above formula (I) are linear, or where possible, branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, iso-octyl, 2-ethylhexyl, tert-octyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl (lauryl), n-tridecyl, n-tetradecyl (myristyl), n-pentadecyl, n-hexadecyl (cetyl), n-octadecyl etc.

The polymer compositions wherein the compounds (I), as defined above, are present, attain the desirable ratings related established flame retardant test methods, especially in polyolefin compositions.

This compound (I) is preferably contained in the flame retardant compositions according to the invention in an amount from about 0.005-90.0 wt. %, preferably about 0.02-20.0 wt. %, most preferably between 0.10-15.0 wt.-%, based on the total weight of the composition.

The term polymer and substrate comprises within its scope thermoplastic and duro-plastic polymers and thermosets.

A list of suitable thermoplastic polymers is given below:

-   -   1. Polymers of monoolefins and diolefins, for example         thermoplastic polyolefins (TPO), such as polypropylene,         polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,         polyvinylcyclohexane, polyisoprene or polybutadiene, as well as         polymers of cycloolefins, for instance of cyclopentene or         norbornene, polyethylene (which optionally can be cross linked),         for example high density polymethylene (HDPE), high density and         high molecular weight polyethylene (HDPE-HMW), high density and         ultrahigh molecular weight polyethylene (HDPE-UHMW), medium         density polyethylene (MDPE), low density polyethylene (LDPE),         linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).         Polyolefins, i.e. the polymers of monoolefins exemplified in the         preceding paragraph, preferably polyethylene and polypropylene,         can be prepared by different and especially by the following         methods:         -   a) Radical polymerisation (normally under high pressure and             at elevated temperature).         -   b) Catalytic polymerisation using a catalyst that normally             contains one or more than one metal of groups IVb, Vb, VIb             or VIII of the Periodic Table. These metals usually have one             or more than one ligand, typically oxides, halides,             alcoholates, esters, ethers, amines, alkyls, alkenyls and/or             aryls that may be either α- or π-bond coordinated. These             metal complexes may be in the free form or fixed on             substrates, typically on activated magnesium chloride,             titanium(III) chloride, and alumina or silicon oxide. These             catalysts may be soluble or insoluble in the polymerisation             medium. The catalysts can be used by themselves in the             polymerisation or further activators may be used, typically             metal alkyls, metal hydrides, metal alkyl halides, metal             alkyl oxides or metal alkyloxanes, said metals being             elements of groups Ia, IIa and/or IIIa of the Periodic             Table. The activators may be modified conveniently with             further ester, ether, and amine or silyl ether groups. These             catalyst systems are usually termed Phillips, Standard Oil             Indiana, Ziegler-Natta), TNZ (DuPont), metallocene or single             site catalysts (SSC).     -   2. Mixtures of the polymers mentioned under 1), for example         mixtures of polypropylene with polyisobutylene, polypropylene         with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of         different types of polyethylene (for example LDPE/HDPE).     -   3. Copolymers of monoolefins and diolefins with each other or         with other vinyl monomers, for example ethylene/propylene         copolymers, linear low density polyethylene

(LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers, where the 1-olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vinylcyclo-hexene copolymers, ethylene/alkyl acrylate copolymers, such as ethylene-n-butyl acrylate or methacrylate, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

-   -   4. Hydrocarbon resins (for example C₅-C₉) including hydrogenated         modifications thereof (e.g. tackifiers) and mixtures of         polyalkylenes and starch;

The homopolymers and copolymers mentioned above may have a stereo structure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereo block polymers are also included.

-   -   5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).     -   6. Aromatic homopolymers and copolymers derived from vinyl         aromatic monomers including styrene, α-methylstyrene, all         isomers of vinyl toluene, especially p-vinyl toluene, all         isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl         naphthalene, and vinyl anthracene, and mixtures thereof.         Homopolymers and copolymers may have a stereo structure         including syndiotactic, isotactic, hemi-isotactic or atactic;         where atactic polymers are preferred. Stereo block polymers are         also included;         -   a) Copolymers including aforementioned vinyl aromatic             monomers and comonomers selected from ethylene, propylene,             dienes, nitriles, acids, maleic anhydrides, maleimides,             vinyl acetate and vinyl chloride or acrylic derivatives and             mixtures thereof, for example styrene/butadiene,             styrene/acrylonitrile, styrene/ethylene (interpolymers),             styrene/alkyl methacrylate, styrene/butadiene/alkyl             acrylate, styrene/butadiene/alkyl methacrylate,             styrene/maleic anhydride, styrene/acrylonitrile/methyl             acrylate; mixtures of high impact strength of styrene             copolymers and another polymer, for example a polyacrylate,             a diene polymer or an ethylene/propylene/diene terpolymer;             and block copolymers of styrene such as             styrene/butadiene/styrene, styrene/iso-prene/styrene,             styrene/ethylene/butylene/styrene or             styrene/ethylene/propy-lene/styrene.         -   b) Hydrogenated aromatic polymers derived from hydrogenation             of polymers mentioned under 6.), especially including             polycyclohexylethylene (PCHE) prepared by hydrogenating             atactic polystyrene, often referred to as             polyvinylcyclohexane (PVCH).         -   c) Hydrogenated aromatic polymers derived from hydrogenation             of polymers mentioned under 6a). Homopolymers and copolymers             may have a stereo structure including syndiotactic,             isotactic, hemi-isotactic or atactic; where atactic polymers             are preferred. Stereo block polymers are also included.     -   7. Graft copolymers of vinyl aromatic monomers, such as styrene         or α-methylstyrene, for example styrene on polybutadiene,         styrene on polybutadiene-styrene or poly-butadiene-acrylonitrile         copolymers; styrene and acrylonitrile (or methacrylonitrile) on         polybutadiene; styrene, acrylonitrile and methyl methacrylate on         polybutadiene; styrene and maleic anhydride on polybutadiene;         styrene, acrylonitrile and maleic anhydride or maleimide on         polybutadiene; styrene and maleimide on polybutadiene; styrene         and alkyl acrylates or methacrylates on polybutadiene; styrene         and acrylonitrile on ethylene/propylene/diene terpolymers;         styrene and acrylonitrile on polyalkyl acrylates or polyalkyl         methacrylates, styrene and acrylonitrile on acrylate/butadiene         copolymers, as well as mixtures thereof with the copolymers         listed under 6), for example the copolymer mixtures known as         ABS, MBS, ASA or AES polymers.     -   8. Halogen-containing polymers such as polychloroprene,         chlorinated rubbers, chlorinated and brominated copolymer of         isobutylene-isoprene (halobutyl rubber), chlorinated or         sulphochlorinated polyethylene, copolymers of ethylene and         chlorinated ethylene, epichlorohydrin homo- and copolymers,         especially polymers of halogen-containing vinyl compounds, for         example polyvinyl chloride, polyvinylidene chloride, polyvinyl         fluoride, polyvinylidene fluoride, as well as copolymers thereof         such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl         acetate or vinylidene chloride/vinyl acetate copolymers.     -   9. Polymers derived from α,β-unsaturated acids and derivatives         thereof such as polyacrylates and polymethacrylates; polymethyl         methacrylates, polyacrylamides and polyacrylonitriles,         impact-modified with butyl acrylate.     -   10. Copolymers of the monomers mentioned under 9) with each         other or with other unsaturated monomers, for example         acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate         copolymers, acrylonitrile/alkoxyalkyl acrylate or         acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl         methacrylate/butadiene terpolymers.     -   11. Polymers derived from unsaturated alcohols and amines or the         acyl derivatives or acetals thereof, for example polyvinyl         alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl         benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl         phthalate or polyallyl melamine; as well as their copolymers         with olefins mentioned in 1 above.     -   12. Homopolymers and copolymers of cyclic ethers such as         polyalkylene glycols, polyethylene oxide, polypropylene oxide or         copolymers thereof with bisglycidyl ethers.     -   13. Polyacetals such as polyoxymethylene and those         polyoxymethylenes, which contain ethylene oxide as a co-monomer;         polyacetals modified with thermoplastic polyurethanes, acrylates         or MBS.     -   14. Polyphenylene oxides and sulphides, and mixtures of         polyphenylene oxides with styrene polymers or polyamides.     -   15. Polyamides and co-polyamides derived from diamines and         dicarboxylic acids and/or from aminocarboxylic acids or the         corresponding lactams, for example polyamide 4, polyamide 6,         polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11,         polyamide 12, aromatic polyamides starting from m-xylene diamine         and adipic acid; polyamides prepared from hexamethylenediamine         and isophthalic or/and terephthalic acid and with or without an         elastomer as modifier, for example         poly-2,4,4,-trimethylhexamethylene terephthalamide or         poly-m-phenylene isophthalamide; and also block copolymers of         the aforementioned polyamides with polyolefins, olefin         copolymers, ionomers or chemically bonded or grafted elastomers;         or with polyethers, e.g. with polyethylene glycol, polypropylene         glycol or polytetramethylene glycol; as well as polyamides or         co-polyamides modified with EPDM or ABS; and poly-amides         condensed during processing (RIM polyamide systems).     -   16. Polyureas, polyimides, polyamide imides, polyether imides,         polyester imides, polyhydantoins and polybenzimidazoles.     -   17. Polyesters derived from dicarboxylic acids and diols and/or         from hydroxycarboxylic acids or the corresponding lactones, for         example polyethylene terephthalate, polybutylene terephthalate,         poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene         naphthalate (PAN) and polyhydroxybenzoates, as well as block         co-polyether esters derived from hydroxyl-terminated polyethers;         and also polyesters modified with polycarbonates or MBS.     -   18. Polyketones.     -   19. Polysulphones, polyether sulphones and polyether ketones.     -   20. Blends of the aforementioned polymers (polyblends), for         example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS,         PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE,         PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR,         POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers,         PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.     -   21. Polycarbonates that correspond to the general formula:

-   -   Such polycarbonates are obtainable by interfacial processes or         by melt processes (catalytic transesterification). The         polycarbonate may be either branched or linear in structure and         may include any functional substituents. Polycarbonate         copolymers and polycarbonate blends are also within the scope of         the invention. The term polycarbonate should be interpreted as         inclusive of copolymers and blends with other thermoplastics.         Methods for the manufacture of polycarbonates are known, for         example, from U.S. Pat. Nos. 3,030,331; 3,169,121; 4,130,458;         4,263,201; 4,286,083; 4,552,704; 5,210,268; and 5,606,007. A         combination of two or more polycarbonates of different molecular         weights may be used.     -   Preferred are polycarbonates obtainable by reaction of a         diphenol, such as bisphenol A, with a carbonate source. Examples         of suitable diphenols are:

4,4′-(2-norbornylidene)bis(2,6-dichlorophenol); or fluorene-9-bisphenol:

-   -   The carbonate source may be a carbonyl halide, a carbonate ester         or a haloformate. Suitable carbonate halides are phosgene or         carbonylbromide. Suitable carbonate esters are         dialkylcarbonates, such as dimethyl- or diethylcarbonate,         diphenyl carbonate, phenyl-alkylphenylcarbonate, such as         phenyl-tolylcarbonate, dialkylcarbonates, such as dimethyl- or         diethylcarbonate, di-(halophenyl)carbonates, such as         di-(chlorophenyl)carbonate, di-(bromophenyl)carbonate,         di-(tri-chlorophenyl)carbonate or di-(trichlorophenyl)carbonate,         di-(alkylphenyl)carbonates, such as di-tolylcarbonate,         naphthylcarbonate, dichloronaphthylcarbonate and others.     -   The polymer substrate mentioned above, which comprises         polycarbonates or polycarbonate blends is a         polycarbonate-copolymer, wherein         isophthalate/terephtha-late-resorcinol segments are present.         Such polycarbonates are commercially available, e.g. Lexan® SLX         (General Electrics Co. USA). Other polymeric substrates of         component b) may additionally contain in the form as admixtures         or as copolymers a wide variety of synthetic polymers including         polyolefins, polystyrenes, polyesters, polyethers, polyamides,         poly(meth)acrylates, thermoplastic polyurethanes, polysulphones,         polyacetals and PVC, including suitable compatibilizing agents.         For example, the polymer substrate may additionally contain         thermoplastic polymers selected from the group of resins         consisting of polyolefins, thermoplastic polyurethanes, styrene         polymers and copolymers thereof. Specific embodiments include         polypropylene (PP), polyethylene (PE), polyamide (PA),         polybutylene terephthalate (PBT), polyethylene terephthalate         (PET), glycol-modified polycyclohexylenemethylene terephthalate         (PCTG), polysulphone (PSU), polymethylmethacrylate (PMMA),         thermoplastic polyurethane (TPU),         acrylonitrile-butadiene-styrene (ABS),         acrylonitrile-styrene-acrylic ester (ASA),         acrylonitrile-ethylene-propylene-styrene (AES), styrene-maleic         anhydride (SMA) or high impact polystyrene (HIPS).

A preferred embodiment of the invention relates to the use of NOR-HALS compounds (I) in thermoplastic polymers. Preferred thermoplastic polymers include polyamides, polyesters and polycarbonates.

Another preferred embodiment of the invention relates to a composition, wherein component c) is a duroplastic polymer substrate of the polyepoxide type.

A particularly preferred embodiment of the invention relates to the use of a NOR-HALS compound (I), wherein R₁ and R₂, independently of one another, represent n-butyl, n-undecyl or n-octadecyl, for inducing flame retardancy in polymers.

A highly preferred embodiment of the invention relates to the use of a NOR-HALS compound (I), wherein R₁ and R₂ represent n-undecyl, for inducing flame retardancy in polymers.

A further embodiment of the invention relates to a composition, which comprises

-   -   a) At least one NOR-HALS compound of the formula

-   -   Wherein     -   R₁ and R₂ represent C₁-C₃₀alkyl;     -   b) At least one flame retardant compound selected from the group         consisting of tris(tribromoneopentyl)phosphate:

-   -   resorcinol-bis-diphenylphosphate:

-   -   pentaerythritol-di-methyl phosphonate:

-   -   guanidine phenylphosphonate, melamine phenylphosphonate,         dimethylaluminium phosphinate, methyl-ethylaluminiumphosphinate,         diethylaluminiumphosphinate,         poly-[2,4-(piperazine-1,4-yl)-6-morpholine-4-yl)-1,3,5-triazine]         and ammonium polyphosphate; and     -   c) A polymer substrate.

The use of the composition defined above for inducing the flame retardancy in polymers is also subject matter of the present invention.

Another preferred embodiment relates to a composition, which comprises

-   -   a) At least one NOR-HALS compound (I), wherein R₁ and R₂         represent n-undecyl;     -   b) At least one flame retardant compound selected from the group         consisting of tris(tribromoneopentyl)phosphate,         resorcinol-bis-di phenylphosphate, pentaerythritol-di-methyl         phosphonate, guanidine phenylphosphonate, melamine         phenylphosphonate, dimethylaluminium phosphinate,         methyl-ethylaluminiumphosphinate, diethylaluminiumphosphinate,         poly-[2,4-(piperazine-1,4-yl)-6-morpholine-4-yl)-1,3,5-triazine]         and aluminum polyphosphate; and     -   c) A polymer substrate.

The combination of the NOR-HALS (I) and the additional flame retardants defined above is preferably contained in the flame retardant compositions according to the use defined above in an amount from about 0.005-90.0 wt. %, preferably about 0.02-20.0 wt. %, most preferably between 0.10-15.0 wt.-%, based on the total weight of the composition.

The instant invention further pertains to the use of compounds (I) in flame retardant compositions and to the above-defined compositions which comprise, in addition to the components defined above, optional components, such as additional flame retardants and/or further additives selected from the group consisting of tetraalkylpiperidine additives, smoke suppressants, polymer stabilizers, fillers, reinforcing agents and so-called anti-dripping agents that reduce the melt flow of thermoplastic polymers and reduce the formation of drops at higher temperatures.

Such additional flame retardants are phosphorus containing flame retardants, for example selected from the group consisting of phosphorus and/or nitrogen containing flame retardants, organo-halogen containing flame retardants and inorganic flame retardants.

Phosphorus containing flame retardants are, for example, resorcinol phenylphosphate oligomer (Fyrolflex® RDP, Akzo Nobel), triphenyl phosphate, bisphenol A phenylphosphate oligomer (Fyrolflex® BDP), tris(2,4-di-tert-butylphenyl)phosphate, ethylenediamine diphosphate (EDAP), tetra(2,6-dimethylphenyl) resorcinol diphosphate, diethyl-N,N-bis(2-hydroxyethyl)-aminomethyl phosphonate, hydroxyalkyl esters of phosphorus acids, salts of hypophosphoric acid (H₃PO₂), particularly the Ca²⁺, Zn²⁺, or Al³⁺ salts, tetrakis(hydroxymethyl)phosphonium sulphide, triphenylphosphine, triphenyl phosphine oxide, tetraphenyldiphosphine monoxide, phosphazenes and 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and its derivatives, such as 2-(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)-1,4-benzenediol.

Nitrogen containing flame retardants are, for example, isocyanurate flame retardants, such as polyisocyanurate, esters of isocyanuric acid or isocyanurates. Representative examples are hydroxyalkyl isocyanurates, such as tris-(2-hydroxyethyl)isocyanurate, tris(hydroxymethyl)isocyanurate, tris(3-hydroxy-n-proyl)isocyanurate or triglycidyl isocyanurate.

Nitrogen containing flame-retardants furthermore include melamine-based flame retardants. Representative examples are: melamine cyanurate, melamine borate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, dimelamine phosphate and dimelamine pyrophosphate.

Further examples are: benzoguanamine, allantoin, glycoluril, urea cyanurate, ammonium polyphosphate, and a condensation product of melamine from the series melem, melam, melon and/or a higher condensed compound or a reaction product of melamine with phosphoric acid or a mixture thereof.

Representative organo-halogen flame retardants are, for example:

Polybrominated diphenyl oxide (DE-60F, Chemtura Corp.), decabromodiphenyl oxide (DBDPO; Saytex® 102E), tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate (PB 370®, FMC Corp.), tris(2,3-dibromopropyl)phosphate, tris(2,3-dichloropropyl)phosphate, chlorendic acid, tetrachlorophthalic acid, tetrabromophthalic acid, polychloroethyl triphosphonate mixture, tetrabromobisphenol A bis(2,3-dibromopropyl ether) (PE68), brominated epoxy resin, ethylene-bis(tetrabromophthalimide) (Saytex® BT-93), bis(hexachlorocyclopentadieno)cyclooctane (Declorane Plus®), chlorinated paraffins, octa-bromodiphenyl ether, 1,2-bis(tribromophenoxy)ethane (FF680), tetrabromo-bisphenol A (Saytex® RB100), ethylene bis-(dibromo-norbornanedicarboximide) (Saytex® BN-451), bis-(hexachlorocyclopentadieno) cyclooctane, PTFE, tris-(2,3-dibromopropyl)-isocyanurate, and ethylene-bis-tetrabromophthalimide.

The organohalogen flame retardants mentioned above are routinely combined with an inorganic oxide synergist. Most common for this use are zinc or antimony oxides, e.g. Sb₂O₃ or Sb₂O₅. Boron compounds are suitable, too.

Representative inorganic flame retardants include, for example, aluminium trihydroxide (ATH), boehmite (AlOOH), magnesium dihydroxide (MSH), hydrotalcite, zinc borates, CaCO₃, (organically modified) layered silicates, (organically modified) layered double hydroxides, and mixtures thereof.

The above-mentioned additional flame retardant classes are advantageously contained in the composition of the invention in an amount from about 0.5% to about 75.0% by weight of the organic polymer substrate; for instance about 10.0% to about 70.0%; for example about 25.0% to about 65.0% by weight, based on the total weight of the composition.

According to another embodiment, the invention relates to compositions which additionally comprise as additional component so-called anti-dripping agents.

These anti-dripping agents reduce the melt flow of the thermoplastic polymer and inhibit the formation of drops at high temperatures. Various references, such as U.S. Pat. No. 4,263,201, describe the addition of anti-dripping agents to flame retardant compositions.

Suitable additives that inhibit the formation of drops at high temperatures include glass fibres, polytetrafluoroethylene (PTFE), high temperature elastomers, carbon fibres, glass spheres and the like.

The addition of polysiloxanes of different structures has been proposed in various references; cf. U.S. Pat. Nos. 6,660,787, 6,727,302 or 6,730,720.

According to a further embodiment, the invention relates to compositions which additionally comprise as additional components fillers and reinforcing agents. Suitable fillers are, for example, glass powder, glass microspheres, silica, mica, wollastonite and talcum.

Stabilizers are preferably halogen-free and selected from the group consisting of nitroxyl stabilizers, nitrone stabilizers, amine oxide stabilizers, benzofuranone stabilizers, phosphite and phosphonite stabilizers, quinone methide stabilizers and monoacrylate esters of 2,2′-alkylidenebisphenol stabilizers.

As mentioned above, the composition according to the invention may additionally contain one or more conventional additives, for example selected from the group consisting of pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic co-stabilizers, metal passivators, metal oxides, organophosphorus compound, UV-absorbers and further light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate and UV absorbers of the 2-hydroxy-benzophenone, 2-(2′-hydroxyphenyl)benzotriazole and/or 2-(2-hydroxyphenyl)-1,3,5-triazine and benzoate groups, such as 2,4-Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate (TINUVIN 120) or hexadecyl 3,5-bis-tert-butyl-4-hydroxybenzoate (Cytec Cyasorb®UV 2908.

Preferred additional additives for the compositions as defined above are processing stabilizers, such as the above-mentioned phosphites and phenolic antioxidants, and light stabilizers, such as benzotriazoles. Preferred specific antioxidants include octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1076), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (IRGANOX 1010), tris(3,5-ditert-butyl-4-hydroxyphenyl)isocyanurate (IRGANOX 3114), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (IRGANOX 1330), triethyleneglycol-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (IRGANOX 245), and N,N′-hexane-1,6-diyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] (IRGANOX 1098). Specific processing stabilizers include tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168), 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (IRGAFOS 126), 2,2′,2″-nitrilo[triethyl-tris(3,3′,5,5′-tetra-tert-butyl-1,1-biphenyl-2,2′-diyl)]phosphite (IRGAFOS 12), and tetrakis(2,4-di-tert-butylphenyl)-[1,1-biphenyl]-4,4′-diylbisphosphonite (IRGAFOS P-EPQ). Specific light stabilizers include 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (TINUVIN 234), 2-(5-chloro(2H)-benzotriazole-2-yl)-4-(methyl)-6-(tert-butyl)phenol (TINUVIN 326), 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (TINUVIN 329), 2-(2H-benzotriazole-2-yl)-4-(tert-butyl)-6-(sec-butyl)phenol (TINUVIN 350), 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) (TINUVIN 360), and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol (TINUVIN 1577), 2-(2′-hydroxy-5′-methylphenyl)benzotriazole (TINUVIN P), 2-hydroxy-4-(octyloxy)benzophenone (CHI-MASSORB 81), 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis-{[(2′-cyano-3′,3′-diphenylacryloyl)oxy]methyl}-propane (UVINUL 3030, BASF), ethyl-2-cyano-3,3-di-phenylacrylate (UVINUL 3035, BASF), and (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate (UVINUL 3039, BASF).

According to a further embodiment the compositions comprise as an optional component the additional flame retardants defined above and additives selected from the group consisting of polymer stabilizers and tetraalkylpiperidine derivatives.

Representative examples of tetraalkylpiperidine derivatives are selected from the group consisting of

-   -   1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine,     -   bis(1-Octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,     -   2,4-bis[(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hy-droxyethylamino-s-triazine,     -   bis(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,     -   2,4-bis[(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazine,     -   1-(2-Hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,     -   1-(2-Hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,     -   1-(2-Hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethyl-piperidine,     -   bis(1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)         sebacate,     -   bis(1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)         adipate,     -   2,4-bis{N-[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine,

The reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazine with N,N′-bis(3-aminopropyl)ethylenediamine),

-   -   2,4-bis[(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino)-s-triazine,     -   The oligomeric compound which is the condensation product of         4,4′-hexame-thylenebis(amino-2,2,6,6-tetramethylpiperidine) and         2,4-dichloro-6-[(1-cyclo-hexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine         end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine,     -   The compound of the formula

-   -   and the compound of the formula

in which n is a numeral from 1 to 15.

The additives mentioned above are preferably contained in an amount of 0.01 to 10.0%, especially 0.05 to 5.0%, relative to the weight of the polymer substrate of Component c).

The incorporation of the components defined above into the polymer component is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil. The additive components may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed additive or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc.), e.g. as a dry mixture or powder, or as a solution or dispersion or suspension or melt.

The addition of the additive components to the polymer substrate can be carried out in customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.

The process is preferably carried out in an extruder by introducing the additive during processing.

Particularly preferred processing machines are single-screw extruders, contra-rotating and co-rotating twin-screw extruders, planetary-gear extruders, ring extruders or co-kneaders. Processing machines provided with at least one gas removal compartment can be used to which a vacuum can be applied.

Suitable extruders and kneaders are described, for example, in Handbuch der Kunststoffextrusion, Vol. 1 Grundlagen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7).

For example, the screw length is 1-60 screw diameters, preferably 35-48 screw diameters. The rotational speed of the screw is preferably 10-600 rotations per minute (rpm), preferably 25-300 rpm.

The maximum throughput is dependent on the screw diameter, the rotational speed and the driving force. The process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.

If a plurality of components is added, these can be premixed or added individually.

The additive components and optional further additives can also be added to the polymer in the form of a master batch (“concentrate”) which contains the components in a concentration of, for example, about 1.0% to about 80.0% and preferably 2.0% to about 60.0% by weight incorporated in a polymer. The polymer is not necessarily of identical structure than the polymer where the additives are added finally. In such operations, the polymer can be used in the form of powder, granules, solutions, and suspensions or in the form of lattices.

The additive components can also be added to the polymer in the form of a master batch (“concentrate”) which contains the components in a concentration of, for example, about 1.0% to about 80.0% and preferably 2.0% to about 60.0% by weight incorporated in a polymer. The polymer is not necessarily of identical structure than the polymer where the additives are added finally. In such operations, the polymer can be used in the form of powder, granules, solutions, and suspensions or in the form of lattices. Incorporation can take place prior to or during the shaping operation. The materials containing the additives of the invention described herein preferably are used for the production of molded articles, for example injection molded or roto-molded articles, injection molded articles, profiles and the like, and fibres, spun melt non-woven, films or foams.

A preferred embodiment relates to a process for inducing the flame retardancy in polymers, which comprises adding to a polymer substrate a combination of

-   -   a) At least one NOR-HALS compound of the formula

-   -   Wherein     -   R₁ and R₂ represent C₁-C₃₀alkyl; with     -   b) At least one flame retardant compound selected from the group         consisting of tris(tribromoneopentyl)phosphate,         resorcinol-bis-di phenylphosphate, pentaerythritol-di-methyl         phosphonate, guanidine phenylphosphonate, melamine         phenylphosphonate, dimethylaluminium phosphinate,         methyl-ethyl-aluminiumphosphinate, diethylaluminiumphosphinate,         poly-[2,4-(piperazine-1,4-yl)-6-morpholine-4-yl)-1,3,5-triazine]         and ammonium polyphosphate.

The polymer substrate suitable for inducing flame retardancy has been described above.

The following Examples illustrate the invention:

A) METHODS

The following standard test methods are used to evaluate the performance of FR-1 as flame retardant:

DIN 4102-Part 1

The specimen is positioned vertically and the ignition flame is applied at the lower edge of the specimen (edge ignition test).

Classification is based on the time for flames to spread 150 mm of the specimen.

If the flame does not reach the 150 mm reference mark within 20 seconds, the tested film passes the test and is classified B2.

UL 94-VTM and UL 94-V

A flame is applied twice to the lower end of the test specimen positioned vertically.

UL 94-VTM is a well-known test for classifying the flame retardancy of very thin material in 3 classes VTM-0, VTM-1 and VTM-2. The best rating is VTM-0.

UL 94 test for Flammability of Plastic Materials for Parts in Devices and Appliances, 5th edition, Oct. 29, 1996. Ratings according to the UL 94 V test are compiled in the following table (time periods are indicated for one specimen):

TABLE Rating After flame time [sec] Burning drips Burn to clamp V-0 <10 No No V-1 <30 No No V-2 <30 Yes No n.c. <30 Yes n.c. >30 No n.c.: not classified FR-1

R₁, R₂: n-undecyl

B) APPLICATION EXAMPLES Example 1

Flame Retardancy of Fiber Grade Polypropylene (MFI 25) Containing 1% of FR-1

PP Film Manufacture:

Fiber grade polypropylene (Moplen® HP 552 (Basell)) is dry blended with 1% of FR-1 and melt compounded into pellets on a co-rotating twin-screw extruder type Berstorff 32D (lab size twin screw extruder, 25 mm screw diameter, 9 heating zones) at a temperature T_(max) of 230° C.

The pelletized fully formulated resin is cast at a maximum temperature T_(max) of 200° C. into 250 μm films using a cast film equipment Collin CR-136/350 coupled with an extruder Collin E 30 M.

Produced films and concentration of additive are listed in Table 1:

TABLE 1 Concentration of added additive in the PP film Film No. Additive Film 1 No addition Film 2 1% FR-1 Performance of FR-1 as Flame Retardant:

TABLE 2 Flame test on 250 μm PP cast films according to modified DIN 4102-Part 1 (edge ignition) Burning Damaged Burning time length drips paper DIN 4102-B2 Film No. [sec] [mm] ignition ^(f)) Rating Film 1 33 190 yes not classified Film 2 8 62 no B2 ^(f)) Rated “yes”, if the burning drips ignite the paper placed underneath the test specimen according to the DIN 4102-Part 1 test norm.

The burning time of Film 2 containing 1% FR-1 decreases significantly in comparison to Film 1. Film 2 is classified as B2. FR-1 contributes to lower the burning time and the damaged length and, therefore, increases flame retardancy of polypropylene.

TABLE 3 Flame test on 250 μm PP cast films according to UL94-VTM Average flaming time ^(a)) Specimen burnt UL94-VTM Film No. [sec] to holding clamp Rating Film 1 31 Yes not classified Film 2 13 No VTM-2 ^(a)) Average flaming time per specimen and after maximum 2 ignitions

The efficacy of FR-1 as a flame retardant is demonstrated by a lower average flaming time, with no specimen burnt to the clamp and VTM-2 classification.

Example 2

Flame retardancy of Cast Film Grade Polypropylene (MP 8) Containing 1% of FR-1

PP Film Manufacture:

Fiber grade polypropylene (RD204CF (Borealis)) is dry blended with 1% of FR-1 and melt compounded into pellets on a co-rotating twin-screw extruder type Berstorff 46D (lab size twin screw extruder, 25 mm screw diameter at a temperature T_(max) of 250° C.

The pelletized fully formulated resin is cast at a maximum temperature T_(max) of 230° C. into 250 μm films using a cast film equipment Collin CR-136/350 coupled with an extruder Collin E 30 M.

Produced films and concentration of additive are listed in Table 4.

TABLE 4 Concentration of added additive in the PP film Film No. Additive Film 1 No addition Film 2 1% FR-1 Performance of FR-1 as Flame Retardant:

TABLE 5 Flame test on 250 μm PP cast films according to modified DIN 4102-Part 1 (edge ignition) Burning Damaged Burning time length drips paper DIN 4102-B2 Film No. [sec] [mm] ignition ^(f)) Rating Film 1 30 190 yes not classified Film 2 10 77 no B2 ^(f)) Rated “yes”, if the burning drips ignite the paper placed underneath the test specimen according to the DIN 4102-Part 1 test norm.

The burning time of Film 2 containing 1% FR-1 decreases significantly in comparison with Film 1. Film 2 is classified B2. FR-1 contributes to lower the burning time and the damaged length and, therefore, increases the flame retardancy of polypropylene.

TABLE 6 Flame test on 250 μm PP cast films according to UL94-VTM Average flaming time ^(a)) Specimen burnt UL94-VTM Film No. [sec] to holding damp Rating Film 1 27 Yes not classified Film 2 7 No VTM-2 ^(a)) Average flaming time per specimen and after maximum of 2 ignitions

The efficacy of FR-1 as a flame retardant is demonstrated by a lower average flaming time, with no specimen burnt to the clamp and VTM-2 classification.

Example 3

Flame Retardancy of TPO (Thermoplastic Polyolefin) Membrane Containing 0.8% of FR-1

TPO 1 mm Film Manufacture:

Roofing membrane grade thermoplastic polyolefin (Hifax® CA 10 A Natural (Lyondell Basell Polymers)) is blended on two roll-mill equipment at 160° C. with 2% titanium dioxide pigment, 0.1% calcium stearate and FR-1 and melt compressed at the temperature of 170° C. into 1 mm plaques by using a hot press. Produced plaques and concentration of additives are listed in Table 7.

TABLE 7 Concentration of added additive in the TPO Plaques Film No. Additive Plaque 1 No FR-1 Plaque 2 0.8% FR-1 The Test Method According to DIN 4102-Part 1 is Used to Evaluate the Performance of FR-1 as Flame Retardant:

TABLE 8 Flame test on TPO plaques of 1 mm thickness according to modified DIN 4102-Part 1 (edge ignition) Burning Damaged Burning time length drips paper DIN 4102-B2 Film No. [sec] [mm] ignition f) Rating Plaque 1 75 >150 yes not classified Plaque 2 23 50 yes B2 f) Rated “yes”, if the burning drips ignite the paper placed underneath the test specimen according to the DIN 4102-Part 1 test norm.

The burning time as well as the damaged length of Plaque 2 containing 0.8% FR-1 decreases significantly in comparison to Plaque 1. As a result, Plaque 2 is classified B2.

FR-1 contributes to lower the burning time and the damaged length and therefore increases thermoplastic polyolefin flame retardancy.

Example 4

Flame Retardancy of Injection Molded Grade Polypropylene (MR 25) Containing FR-1 Polymer Component: MOPLEN HP 552 R (Lyondell Basell (PP))

Flame Retardant Components:

ADK STAB LA-81 (ADEKA): bis(1-undecanyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate (FR-1)

Aflammit®TL 1260 (THOR GROUP LIMITED): Pentaerythritol-di-methylphosphonate (FR-2)

PP, FR-1 and FR-2 are premixed in the amounts indicated and melt compounded into pellets on a co-rotating twin-screw extruder Berstorff 32D (lab size twin screw extruder, 25 mm screw diameter) at a maximum temperature T_(max) of 230° C.

UL94-V test specimen of 1.6 mm thickness are prepared by injection molding (Engel EK 65).

TABLE 9 Ref. 1 Ref. 2 Inv. 1 PP 100 84 84 FR-1  1 FR-2 16 15 UL 94 V at 1.6 mm n.c. V-2 V-0

Ref. (Referential Compositions) 1, 2; Inv. (Inventive Composition) 1: Addition of FR-1 increases significantly the FR performance of the composition in comparison to Referential Compositions 1, 2. The efficacy of FR-1 as a flame retardant is demonstrated by V-0 classification.

Example 5

Flame Retardancy of High Density Polyethylene (HDPE) Containing FR-1

HDPE Film Manufacture:

High density polyethylene (Hostalen® ACP 7740 F2 (Lyondell Basell)) is dry blended with FR-1 and melt compounded into pellets on a co-rotating twin-screw extruder type Collin 42D (lab size twin screw extruder, 25 mm screw diameter) at a maximum temperature T_(max) of 210° C.

The pelletized fully formulated resin is extruded and blown at a maximum temperature T_(max) of 230° C. into film by using a blown film extrusion equipment Collin Type 180/400 coupled with an extruder Collin E 30 P.

Produced films and concentration of additive are listed in Table 10.

TABLE 10 Concentration of added additive in HDPE blown films Film No. Film Additive 1 100 μm No addition 2 200 μm No addition 3 100 μm 1.5% FR-1 4 200 μm 1.0% FR-1

TABLE 11 Flame test on 200 μm HDPE blown films according to DIN 4102-Part 1 (edge ignition) Burning Damaged Burning time length drips paper DIN 4102-B2 Film No. [sec] [mm] ignition^(f)) rating 2 31 >150 yes not classified 4 11 71 yes B2 ^(f))Rated “yes”, if the burning drips ignite the paper placed underneath the test specimen according to the DIN 4102-Part 1 test norm.

The burning time of Film 4 containing 1% FR-1 decreases significantly in comparison to Film 2. Film 4 is classified B2. FR-1 contributes to lower the burning time and the damaged length and therefore increases high density polyethylene flame retardancy.

TABLE 12 Flame test on 100 μm HDPE blown films according to UL94-VTM Average flaming time^(a)) Specimen burnt UL94-VTM Film No. [sec] to holding clamp rating 1 16^(b)) Yes not classified 3 7 No VTM-2 ^(a))Average flaming time per specimen and after maximum 2 ignitions ^(b))Specimen completely burnt after the first ignition.

The efficacy of FR-1 as a flame retardant is demonstrated by lower average flaming time, with no specimen burnt to the clamp and VTM-2 classification.

Example 6

Flame Retardancy of Linear Low Density Polyethylene (LLDPE) Containing FR-1

LLDPE Film Manufacture:

Linear low density polyethylene (1002YB (Exxon Mobile)) is dry blended with 1% FR-1 and melt compounded into pellets on a co-rotating twin-screw extruder type Collin 42D (lab size twin screw extruder, 25 mm screw diameter) at a maximum temperature T_(max) of 210° C. The pelletized fully formulated resin is casted at a maximum temperature T_(max) of 190° C. into 100 and 200 μm film by using a cast film equipment Collin CR-136/350 coupled with an extruder Collin E 30 M.

Produced films and concentration of additive are listed in Table 13.

TABLE 13 Concentration of added additive in the LLDPE cast film Film No. Film Additive 1 100 μm without addition 2 200 μm without addition 3 100 μm 1.0% FR-1 4 200 μm 1.0% FR-1

TABLE 14 Flame test on 100 and 200 μm LLDPE cast films according to modified DIN 4102-Part 1 (edge ignition) Burning Damaged Burning time length drips paper DIN 4102-B2 Film No. [sec] [mm] ignition^(f)) Rating Film 1 21 >150 yes not classified (100 μm) Film 2 3 62 no B2 (100 μm) Film 3 32 >150 yes not classified (200 μm) Film 4 6 54 yes B2 (200 μm) ^(f))Rated “yes”, if the burning drips ignite the paper placed underneath the test specimen according to the DIN 4102-Part 1 test norm.

The burning time of Film 2 and 4 containing 1.0% FR-1 decreases significantly in comparison to Film 1 and 3. Film 2 and 4 are classified B2. FR-1 contributes to lower the burning time and the damaged length and, therefore, increases the flame retardancy in low density polyethylene.

TABLE 15 Flame test on 100 and 200 μm LLDPE cast films according to UL94-VTM Average flaming time^(a)) Specimen burnt UL94-VTM Film No. [sec] to holding clamp Rating Film 1 14^(b)) Yes not classified (100 μm) Film 2 4 No VTM-2 (100 μm) Film 3 23^(b)) Yes not classified (200 μm) Film 4 15  No VTM-2 (200 μm) ^(a))Average flaming time per specimen and after maximum 2 ignitions ^(b))Specimen completely burnt after the first ignition.

The efficacy of FR-1 as a flame retardant is demonstrated by lower average flaming time, with no specimen burnt to the clamp and VTM-2 classification. 

The invention claimed is:
 1. A composition, which comprises a) an NOR-HALS compound of the formula

wherein R₁ and R₂ represent n-undecyl; b) at least one flame retardant compound selected from the group consisting of guanidine phenylphosphonate and melamine phenylphosphonate; and c) a polymer substrate.
 2. The composition according to claim 1, wherein said composition further comprises at least one additional flame retardant compound selected from the group consisting of dimethylaluminium phosphinate, methyl-ethyl-aluminiumphosphinate, diethylaluminiumphosphinate, and poly-[2,4-(piperazine-1,4-yl)-6-morpholine-4-yl)-1,3,5 triazine].
 3. The composition according to claim 1, which further comprises at least one additional flame retardant or additive selected from the group consisting of a tetraalkylpiperidine additive, a polymer stabilizer, a filler, a reinforcing agent, a glass fibre, a polytetrafluoroethylene (PTFE), a carbon fibre, and a glass sphere.
 4. The composition according to claim 3, which comprises as an additional flame retardant a nitrogen containing compound selected from the group consisting of melamine polyphosphate, ammonium polyphosphate, melamine ammonium phosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, a condensation product of melamine with phosphoric acid and other reaction products of melamine with phosphoric acid and mixtures thereof.
 5. A process for inducing the flame retardancy in polymers, which comprises adding to a polymer substrate a combination of a) an NOR-HALS compound of the formula

wherein R₁ and R₂ represent n-undecyl; with b) at least one flame retardant compound selected from the group consisting of guanidine phenylphosphonate and melamine phenylphosphonate.
 6. The process according to claim 5, which further comprises adding to said polymer substrate at least one additional flame retardant compound selected from the group consisting of dimethylaluminium phosphinate, methyl-ethyl-aluminiumphosphinate, diethylaluminiumphosphinate, and poly-[2,4-(piperazine-1,4-yl)-6-morpholine-4-yl)-1,3,5 triazine].
 7. The process according to claim 5, which further comprises adding to said polymer substrate at least one additional flame retardant or additive selected from the group consisting of a tetraalkylpiperidine additive, a polymer stabilizer, a filler, a reinforcing agent, a glass fibre, a polytetrafluoroethylene (PTFE), a carbon fibre, and a glass sphere.
 8. The process according to claim 7, which comprises as an additional flame retardant a nitrogen containing compound selected from the group consisting of melamine polyphosphate, ammonium polyphosphate, melamine ammonium phosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, a condensation product of melamine with phosphoric acid and other reaction products of melamine with phosphoric acid and mixtures thereof. 